WO2006109454A1 - Plaque d’impression lithographique photosensible - Google Patents

Plaque d’impression lithographique photosensible Download PDF

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Publication number
WO2006109454A1
WO2006109454A1 PCT/JP2006/305619 JP2006305619W WO2006109454A1 WO 2006109454 A1 WO2006109454 A1 WO 2006109454A1 JP 2006305619 W JP2006305619 W JP 2006305619W WO 2006109454 A1 WO2006109454 A1 WO 2006109454A1
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WO
WIPO (PCT)
Prior art keywords
group
acid
lithographic printing
printing plate
polymer
Prior art date
Application number
PCT/JP2006/305619
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English (en)
Japanese (ja)
Inventor
Koji Hayashi
Eiji Hayakawa
Original Assignee
Kodak Graphic Communications Japan Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kodak Graphic Communications Japan Ltd. filed Critical Kodak Graphic Communications Japan Ltd.
Priority to EP06729586A priority Critical patent/EP1865378A4/fr
Priority to US11/817,876 priority patent/US7883830B2/en
Priority to CN2006800096652A priority patent/CN101167017B/zh
Publication of WO2006109454A1 publication Critical patent/WO2006109454A1/fr

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • B41C1/1016—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials characterised by structural details, e.g. protective layers, backcoat layers or several imaging layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0752—Silicon-containing compounds in non photosensitive layers or as additives, e.g. for dry lithography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/02—Cover layers; Protective layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/04—Intermediate layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/04—Negative working, i.e. the non-exposed (non-imaged) areas are removed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/06—Developable by an alkaline solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers

Definitions

  • the present invention relates to a photosensitive lithographic printing plate, and more particularly to a photosensitive lithographic printing plate provided with a base layer between a support and a photosensitive layer.
  • a negative photosensitive lithographic printing plate for CTP system for example, there is a so-called photopolymer type in which a photosensitive layer mainly composed of a photo-curing resin is formed on a support.
  • the photopolymerization initiator contained in the photosensitive layer is excited upon exposure to generate radicals, whereby the photocurable resin is crosslinked and insolubilized to form an image.
  • the photopolymer type photosensitive lithographic printing plate as described above may have poor adhesion between the photosensitive layer and the support, and therefore, as described in JP-A-2003-57831, It has been proposed to provide an underlayer containing vinylphosphonic acid between the photosensitive layer and the support.
  • the present invention has been made in view of the above-described situation, and an object of the present invention is to provide a means for favorably maintaining the adhesion between the photosensitive layer and the support in the photopolymer type photosensitive lithographic printing plate.
  • An object of the present invention is to provide a photosensitive lithographic printing plate comprising a support and a photosensitive layer containing a photopolymerizable compound, and an ethylenically unsaturated group bonded to a silicon atom between the photosensitive layer and the support. It is achieved by providing an underlayer containing a structural unit having a (co) polymer having a phosphonic acid group. ⁇
  • Y represents a C 1, C 6 alkyl group or a halogen atom
  • k and n are each independently 0 or 1
  • j and m are each independently an integer of 0 to 500, and o, p, q, and r are each independently an integer of 0 to 5, and a group represented by preferable.
  • the phosphonic acid group is preferably
  • R 6 and R 7 each independently represent an alkyl group of H or C! Ce
  • the (co) polymer is
  • R 8 may further have a carboxylic acid group, a carboxylic acid ester group, or an amide group represented by: a hydroxyl group, a Ci Ce alkoxy group or —NH 2 .
  • a (co) polymer having a structural unit having an ethylenically unsaturated group bonded to a silicon atom and a phosphonic acid group is provided between the photosensitive layer and the support.
  • An underlying layer is formed.
  • the ethylenically unsaturated group is in a pendant position relative to the main chain of the (co) polymer and functions as a crosslinking site.
  • the structural unit having an ethylenically unsaturated group bonded to the above silicon atom is as follows:--(COO) k- (CH 2 CH 2 0)] one (CH 2 CH (CH 3 ) 0-(COX) n one ( CH 2 ) .One (CHY) p One (CH 2 ) a- (SiO (R ') (R 2 ) l r -SiR 3 R 5
  • CH 2 — — O— — S— and —NZ— represents a divalent organic group (Z represents an alkyl group of H or C i C 6 ),
  • Y represents a C 6 or C 6 alkyl group or a halogen atom
  • k and n are each independently 0 or 1
  • halogen atom is any one of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the phosphonic acid group is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N
  • R 6 and R 7 are each independently H or, to (indicating an alkyl group of 6 )
  • R 8 may further have a hydroxyl group, a carboxylic acid group represented by ⁇ to (indicating an alkoxy group or 1 NH 2 ), a carboxylic acid ester group, or an amide group.
  • the C 1 C 6 alkyl group is preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
  • C a methyl group or an ethyl group
  • a methoxy group or an ethoxy group is preferable, and a methoxy group is particularly preferable.
  • the above (co) polymer contained in the underlayer can be easily synthesized by a method known in the art, for example, a monomer having an ethylenically unsaturated group bonded to a silicon atom, and phosphonic acid. It can be easily synthesized by radical copolymerization with a monomer having a group.
  • R 1 , R 2 , R 3 , R 4 , R 5 , X, Y are as described above,
  • R 3 represents H or 1 CH 3 ,
  • the (meth) acrylic monomer is obtained by, for example, reacting an ester of (meth) acrylic acid and a polyol with an alkyl isocyanate having an alkoxysilyl group, and subjecting the reaction product to a condensation reaction with a vinylalkoxysilane. Can be synthesized.
  • the alkyl group of the alkyl isocyanate may be substituted with a halogen atom.
  • a condensate of a reaction product of hydroxychetyl (meth) acrylate or polyethylene glycol (metha) acrylate with 3-isocyanate propyl trimethoxysilane and vinyl trimethoxysilane is preferable.
  • the vinyl monomer can be synthesized, for example, by condensing a plurality of molecules of alkoxyvinylsilane in water. Condensation centered on the alkoxysilane site, so when using this monomer to polymerize by radical addition polymerization reaction, there is a concern of insolubilization in any solvent, so-called gelation reaction, but at the time of polymerization Gelation can be prevented by selecting a solvent.
  • vinylphosphonic acid monomer vinylphosphonic acid is particularly preferable.
  • (meth) acrylic monomers represented by the following can be used for radical copolymerization.
  • acrylic acid, methacrylic acid, methacrylamide, and acrylamide are particularly preferable.
  • the ratio of the amount of each monomer used is not particularly limited, but the ratio of the monomer having an ethylenically unsaturated group bonded to a carbon atom is within the range of 0.05 to 50 mol% of all monomers. A certain power is preferable, and the range of 0.05 to 10 mol% is more preferable.
  • the solvent for the radical copolymerization is not particularly limited, but a non-aqueous solvent is preferable, and ethyl acetate is particularly preferable.
  • the initiator for radical copolymerization is not particularly limited, and a known initiator such as azobisisoptyronitrile can be used.
  • the underlayer in the present invention contains the (co) polymer obtained as described above as a main component.
  • the proportion of (co) polymer in the underlayer is preferably
  • the range is from 80 to 100% by mass, more preferably from 90 to 100% by mass, and even more preferably from 95 to 100% by mass.
  • the underlayer can be formed on the support described later by various methods. The following methods are listed as typical underlayer forming methods.
  • the above (co) polymer is dissolved in water, an organic solvent such as methanol, ethanol, methyl ethyl ketone, or a mixed solvent thereof, or a mixed solvent of these organic solvent and water.
  • a base layer is formed by applying the dried solution on a support and drying it.
  • the (co) polymer solution having a concentration of 0.005 to 10% by mass may be applied by various methods.
  • the application means include Barco overnight application, spin coating, and spraying. Any means such as coating or curtain coating may be used.
  • the concentration of the solution is 0.005 to 10% by mass, preferably 0.01% to 4% by mass, and the immersion temperature is 30 C to 803 ⁇ 4, preferably 50 to 70 ° C. Soaking time is 0.1 seconds to 5 minutes, good It is preferably 3 to 30 seconds.
  • the above solutions include basic substances such as ammonia, triethylamine, potassium hydroxide, inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, and nitric acid, organic sulfonic acids such as ditrobenzenesulfonic acid and naphthalenesulfonic acid, and phenylphosphonic acid.
  • PH is adjusted with various organic acidic substances such as organic phosphonic acids such as benzoic acid, coumaric acid and malic acid, and organic chlorides such as naphthenic sulfonyl chloride and benzene sulfonyl chloride.
  • PH 0 to 12 and more preferably in the range of pH 0 to 6.
  • a substance that absorbs ultraviolet light, visible light, infrared light, or the like can be added.
  • the coating amount after drying of the undercoat layer in the invention is 1 ⁇ 100mgZ m 2 is suitably in total, preferably 1. 5 ⁇ 70mg / m 2.
  • the photosensitive lithographic printing plate of the present invention comprises a photosensitive layer on an underlayer, and the photosensitive layer essentially contains a photopolymerizable compound.
  • the photosensitive lithographic printing plate of the present invention is a negative type.
  • the photopolymerizable compound contained in the photosensitive layer in the invention is not particularly limited, but is preferably a compound having an addition-polymerizable ethylenically unsaturated bond.
  • a compound can be arbitrarily selected from compounds having at least one ethylenically unsaturated double bond group that is a photopolymerization terminal, preferably two or more, such as a monomer, a prepolymer, That is, it has a chemical form such as a dimer, trimer and oligomer, or a mixture thereof and a copolymer thereof.
  • Examples of monomers and copolymers thereof include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, Crotonic acid, isocrotonic acid, maleic acid, etc.) and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds.
  • unsaturated carboxylic acids eg, acrylic acid, methacrylic acid, itaconic acid, Crotonic acid, isocrotonic acid, maleic acid, etc.
  • aliphatic polyhydric alcohol compounds e.g, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds.
  • the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate ⁇ , 1,3-butanediol di Acrylates, Tetramethylene Dallyol Diacrylate, Propylene Glycol Diacrylate, Neopentyl Glycol Diacrylate, Trimethylol Propanol Triacrylate, Trimethylol Propane Tri (acryloyloxypropyl) Ether, Trimethylol Ethane Triacrylate Hexanediol acrylate, 1,4-cyclohexanediol acrylate, tetraethylene glycol acrylate, pen erythritol acrylate diacrylate, pen tub erythri Toll ria acrylate, Penyu erythritol tetraacrylate, Dipen erythritol acrylate, Dipen erythrito
  • Methacrylic acid esters include tetramethylene glycol dimethyl acrylate, triethylene glycol dimethyl acrylate, neobenthyl alcohol dimethyl methacrylate, trimethylol propane trimethacrylate, trimethylol ethane trimethacrylate, eth Lenglycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythri Tall dimethacrylate, Pen evening erythritol, Tortome trimming, Pen evening erythritol Tetramethacrylate, Dipen evening erythritol Dimethacrylate, Dipentaerythritol Hexamethacrylate, Dipen evening erythritol pen evening Metachlorate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis (p- (3—methyloxyl-2-hydroxypropoxy)
  • Itaconic acid esters include ethylene glycol diethylate, propylene glycol diethylate, 1, 3 _butanediol diconate, 1,4 monobutanediol diconate, tetramethylene glycol diethylate, pen Evening Erisri Torji Evening Connect, Sorbitol Teutorita Connect, etc.
  • crotonic acid ester examples include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Penton erythritol diisocrotonate, sorbitol tetraisocrotonate, etc.
  • maleic esters examples include ethylene glycol dimaleate, triethylene glycol dimaleate, pen erythritol dimaleate, and sorbitol tetramale. Furthermore, a mixture of the aforementioned ester monomers can also be mentioned.
  • amide monomers of an aliphatic polyvalent amine compound and an unsaturated carboxylic acid include methylene bis-acrylamide, methyl bis-methyl amide, 1,6-hexamethylene bis-amide.
  • the Examples include rylamide, 1,6-hexamethylenebismonomethacrylamide, diethylenetriamine trisacrylamide, xylylenebisacrylamide, and xylylenebismethacrylate.
  • polyisocyanate compounds having two or more isocyanate groups in one molecule such as hexamethylene diisocyanate, and the above unsaturated carboxylic acid and aliphatic polyhydric alcohol compound.
  • a vinylurethane compound containing two or more polymerizable vinyl groups in one molecule to which is added a vinyl monomer containing a hydroxyl group represented by the following general formula (A) or (B) Etc.
  • Q 1 and Q 2 independently represent H or CH 3.
  • Q 1 and Q 2 independently represent H or CH 3 , Q 3 represents one CH 2 0 H.
  • urethane acrylates such as those described in JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, JP-B-52-30490
  • Polyfunctional acrylates such as polyester acrylates and epoxy acrylates obtained by reacting epoxy resin with (meth) acrylic acid can be mentioned.
  • those introduced as photocurable monomers and oligomers in Journal of Japan Adhesion Association Vol. 20, No. 7, pages 300 to 30 (1984) can also be used.
  • the amount of these photopolymerizable compounds used is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, based on all components of the photosensitive layer.
  • the photosensitive layer in the present invention includes:
  • An infrared absorber is a substance whose maximum absorption wavelength is in the infrared region from the near infrared, specifically, the maximum absorption wavelength is 760 ⁇ ! It is a substance in the region of ⁇ 1200nin. Examples of such substances include various pigments or dyes.
  • pigments used in the present invention include commercially available pigments, and the Color Index Handbook, “Latest Pigment Handbook, Japan Pigment Technology Association, 1977”, “Latest Pigment Applied Technology” (CMC Publishing, 1986), “Printing Inks” The pigments described in “Technology” (CMC Publishing, 1984) can be used.
  • pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, and other polymer-bonded dyes.
  • insoluble azo pigments azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments face
  • Use can be made of pigments, isoindolinone pigments, quinophthalone pigments, dyed lake pigments, azine pigments, double-loss pigments, double-mouth pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like.
  • carbon black is particularly preferably used as a material that efficiently absorbs light in the near infrared to infrared region and is economically excellent.
  • a graphite car pump rack having various functional groups and a good dispersibility is commercially available. For example, “Power Cycle Pump Handbook 3rd Edition” (Carbon Black Pp. 167 of the association edition, 1995), and pages described in “1 1 1” of “Characteristics and Optimum Formulation and Utilization Technology of Carbon Black” (Technical Information Association, 1997). Is preferably used.
  • These pigments may be used without surface treatment or may be used after performing known surface treatment.
  • Known surface treatment methods include a method of surface-coating a resin or wax, a method of attaching a surfactant, and a reactive material such as a silane coupling agent, an epoxy compound, or a polyisocyanate bonded to the pigment surface. The method etc. are mentioned. These surface treatment methods are described in “Characteristics and Applications of Metal Stone Walls” (Shobobo), “Latest Pigment Application Technology” (CMC Publishing, 1986), “Printing Ink Technology” (CMC Publishing, 1984). Has been.
  • the particle size of the pigment used in the present invention is 0.01 ⁇ ! It is preferably in the range of 5 micrometers, and more preferably in the range of 0.01 to 5 micrometers.
  • dyes used in the present invention known and commonly used dyes can be used.
  • “Dye Handbook” (edited by the Society of Synthetic Organic Chemistry, published in 1970), “Color Material Engineering Handbook” (edited by Color Material Association, Asakura Shoten) ⁇ , Published in 1989), “Technology dye technology and market” (CMMC, published in 1983), “Chemical Handbook” Applied Chemistry ”(The Chemical Society of Japan, Maruzen Shoten, published in 1986).
  • azo dyes metal chain salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, strong luponium dyes, quinone imine dyes, methine dyes, cyanine dyes, indigo dyes, quinoline dyes, nitro dyes And dyes such as xanthene dyes, thiazine dyes, azine dyes, and oxazine dyes.
  • dyes that efficiently absorb near infrared rays or infrared rays include cyanine dyes, methine dyes, naphthoquinone dyes, squalium dyes, arylpenzo (thio) pyridinium salts, trimethine thiapyrylium salts, and pyrylium compounds. Pentamethine thiopyridium salts, infrared absorbing dyes and the like.
  • a near-infrared absorbing cationic dye represented by the following formula is preferable because the photopolymerization initiator described later efficiently exhibits a polymerization function.
  • D + indicates a cationic dye having absorption in the near infrared region
  • a one indicates an anion.
  • cationic dyes having absorption in the near infrared region examples include cyanine dyes, triarylmethane dyes, amino dyes, diimonium dyes having absorption in the near infrared region.
  • Specific examples of cationic dyes having absorption in the near-infrared region include the following.
  • halogen anion CI0 4 —, PF 6 —, BF, SbF 6 one, CH 3 S0 3 —, CF 3 S0 3 —, C 6 H 5 S0 3 —, CH 3 C 6 H 4 S0 3 _, H0C 6 H 4 S0 3 _, C1C 6 H 4 S0 3 —, and a boron anion represented by the following formula (3).
  • boron anion triphenyl n-butyl boron anion and trinaphthyl n-butyl boron anion are preferable.
  • R 9 , R 1 Q , R 11 and R 12 are each independently an alkyl group, an aryl group, an alkaryl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alicyclic group. Or a saturated or unsaturated heterocyclic group, and at least one of R 9 , R 1 Q , R 11 and R 12 is an alkyl group having 1 to 8 carbon atoms.
  • the cationic dye having absorption in the near infrared region those represented by the following formula (4) are preferable. Since these dyes have a maximum absorption wavelength of 817 to 822 nm, the resulting photosensitive lithographic printing plate is suitable for an exposure machine equipped with an existing near infrared semiconductor laser, and has a molar extinction coefficient of 1 ⁇ 10 5 As described above, the obtained photosensitive lithographic printing plate Sensitivity is improved.
  • X is N (C 2 H 5 ) 2 or N (CH 3 ) 2
  • Y is N (C 2 H 5 ) 2
  • H or 0CH 3
  • Z is One of the represented anions.
  • the infrared absorber is used by selecting at least one suitable pigment or dye capable of absorbing a specific wavelength of the light source described later and adding it to the photosensitive layer.
  • the pigment content is preferably in the range of 0.5 to 15% by mass, particularly preferably in the range of 1 to 10% by mass, based on the total solid content of the photosensitive layer. If the pigment content is less than 0.5% by mass, infrared absorption is insufficient, and if the pigment content exceeds 15% by mass, the amount of heat generated tends to be excessive, which is not preferable.
  • the content of the dye is preferably in the range of 0.5 to 15% by mass, particularly preferably in the range of 1 to 10% by mass, based on the total solid content of the photosensitive layer. If the dye content is less than 0.5% by mass, the infrared absorption is insufficient, and if the dye content exceeds 15% by mass, the infrared absorption substantially reaches saturation and the effect of addition is improved. Absent It is not preferable because it is in a tendency.
  • photopolymerization initiator (b) Depending on the wavelength of the light source used, various photopolymerization initiators known in patent documents, non-patent documents, etc., or a combination system of two or more photopolymerization initiators (photopolymerization initiator) The starting system) can be selected as appropriate and used.
  • a photopolymerization initiator used alone and a system in which two or more photopolymerization initiators are used in combination are collectively referred to simply as “photopolymerization initiator”.
  • organoboron compounds As the photopolymerization initiator, organoboron compounds, onium salts, and lyazine compounds are suitable. These photopolymerization initiators may be used alone or in combination of two or more.
  • the organoboron compound exhibits a function as a polymerization initiator when used in combination with the aforementioned infrared absorber.
  • an ammonium salt of a quaternary boron anion represented by the following formula (2) is preferable.
  • R 9 , R 1 Q , R 11 and R 12 are each independently an alkyl group, an aryl group, an alkaryl group, an aralkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alicyclic group.
  • R 3 , R 1 D , R 11 and R 12 is an alkyl group having 1 to 8 carbon atoms
  • R ) 3 R 14 , R 15 and R 16 are each independently a hydrogen atom, an alkyl group, an aryl group, an aryl group, an alkaryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alicyclic group, or a saturated group.
  • R 15 and R 16 are each independently a hydrogen atom, an alkyl group, an aryl group, an aryl group, an alkaryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alicyclic group, or a saturated group.
  • an unsaturated heterocyclic group Show.
  • tetra-n-butyl ammonium triphenyl boron Tetra-n-butyl ammonium trinaphthyl boron, tetra-n-ptylammonium tri (p- t 1 Ptylphenyl) Boron, Tetramethylammonium n—Butyltriphenylboron, Terramethylammonium n—Butyltrinaphthylboron, Tetramethylammonium n—Yetyltriphenylboron, Tetramethylammonium N-year-old cutyl naphthylboron, tetraethylammonium n —butyltriphenylboron, tetraethylammonium n —butyltrinaphthylhydrogen, trimethylhydrammonium n —butyltriphenylboron , ⁇
  • the above-mentioned organoboron compound is used in combination with the above-mentioned infrared absorber (for example, D + A ") to generate radicals (R ⁇ ) as shown in the following formula (5) by irradiation with infrared rays, and polymerize Can function as an initiator (wherein is a phenyl group, R is an alkyl group having 1 to 8 carbon atoms, and X + is an ammonium ion).
  • the content of the organoboron compound is 0.1 to 1 based on the solid content of the photosensitive layer.
  • a range of 5% by mass is preferred, and a range of 0.5-7% by mass is particularly preferred.
  • the content of the organoboron compound is less than 0.1% by mass, the polymerization reaction is insufficient. If the content of the organoboron compound exceeds 15% by mass, the polymerization reaction will not occur efficiently. If necessary, two or more kinds of (B) organoboron compounds may be used in combination.
  • Onium salt is a salt consisting of a cation having one or more onion ion atoms in its molecule and an anion.
  • onium ions in onium salts include S + in sulfonium, 1 + in jordanium, N + in ammonium, and P + atom in phosphonium.
  • preferable onion ion atoms include S + and 1 +.
  • the structure of the ion salt include triphenylsulfone, derivatives having an alkyl group or aryl group introduced into the benzene ring of the compound, and derivatives having an alkyl group or aryl group introduced into the benzene ring of the compound. It is done.
  • Onion salt anions include halogen anions, C10 4 —, PF 6 —, BF 4 —, SbF, CH 3 S0 3- , CF 3 S0 3- , C 6 H 5 S0 3 —, CH 3 C 6 H 4 S0 3 —, HO C 6 H 4 S0 3 —, C1C 6 H 4 S0 3 , and boron anions represented by the above formula (3).
  • the onium salt a combination of an onium salt having S + in the molecule and an onium salt having 1+ in the molecule is preferable from the viewpoint of sensitivity and storage stability.
  • a polyvalent onium salt having two or more onium ion atoms in one molecule is preferable from the viewpoint of sensitivity and storage stability.
  • two or more ion ions in the cation are linked by a covalent bond.
  • the polyvalent ion salts those having two or more kinds of ion ions in one molecule are preferable, and those having S + and I + in one molecule are more preferable.
  • the polyvalent onium salt those represented by the following formulas (6) and (7) are preferable.
  • the content of the onium salt is preferably in the range of 0.1 to 15% by mass, particularly preferably in the range of 0.5 to 7% by mass, based on the solid content of the photosensitive layer. If the content of the onium salt is less than 0.1% by mass, the polymerization reaction may be insufficient, and the sensitivity and printing durability of the resulting negative photosensitive lithographic printing plate may be insufficient. If the salt content exceeds 15% by mass, the developability of the resulting negative photosensitive lithographic printing plate will deteriorate. If necessary, two or more onium salts may be used in combination. Further, a polyvalent ion salt and a monovalent ion salt may be used in combination.
  • the triazine-based compound is a known polymerization initiator used for radical polymerization, and for example, bis ( ⁇ ⁇ ⁇ lihalomethyl) 1 s- ⁇ lyazine can be suitably used as the photopolymerization initiator.
  • the amount of triazine compound is usually very small. In addition, when the amount is inappropriately large, undesired results such as blocking effective light and crystallization in the photosensitive layer after coating to cause reprecipitation are produced.
  • the content of the triazine compound is preferably used in the range of 0.1 to 15% by mass with respect to the solid content of the photosensitive layer. Especially good results are obtained at 0.5-7% by mass. 619.
  • an organic high molecular polymer that is soluble or swellable in alkaline water is preferably used.
  • the organic polymer polymer that is soluble or swellable in alkaline water include those having an alkali-soluble group (acid group) in the main chain or side chain.
  • an acid group an acid group having a pKa of 0 to 12 or less is preferable, and particularly active amino acids such as carboxylic acid group, phenolic hydroxyl group, sulfonamido group, N-sulfonylcarbamoyl group, and N-acylcarbamoyl group.
  • An imino group is more preferable.
  • organic polymer examples include addition polymers having a carboxylic acid group in the side chain, such as JP-A 59-44615, JP-B 54-34327, JP-B 58-12577, and JP-B. 54-25957, JP 54-92723, JP 59-53836, JP 59-7 1048, ie, methacrylic acid copolymer, acrylic acid copolymer Polymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, acidic cellulose derivatives having a carboxylic acid group in the side chain, addition weights having a hydroxyl group A compound obtained by adding a cyclic acid anhydride to the polymer, polyvinyl pyrrolidone, polyethylene oxide, and an alcohol-soluble polyamide that can increase the strength of the cured film 2, 2-bis (4-hydroxyphenyl) monopropane Epi And chlorohydrin polyether.
  • These polymer polymers can improve the strength of the film made of a binder-resin by introducing a radical reactive group into the side chain.
  • functional groups that can undergo an addition polymerization reaction include ethylenically unsaturated bond groups, amino groups, and epoxy groups.
  • functional groups that can become radicals upon irradiation with light include mercapto groups, thiol groups, halogen atoms, and doriadin.
  • Structure, onium salt structure, and the like, and examples of the polar group include a carboxyl group and an imide group.
  • an ethylenically unsaturated bond group such as an acryl group, a methacryl group, a allyl group, and a styryl group is particularly preferable, but an amino group, a hydroxy group, a phosphonic acid group, and a phosphoric acid group.
  • a functional group selected from a strong rubermoyl group, an isocyanate group, a ureido group, a ureylene group, a sulfonic acid group, and an ammonio group can also be used.
  • the binder resin used preferably has an appropriate molecular weight and acid value.
  • the weight average molecular weight is 5000 to 300,000, and the acid value is 20 to 200.
  • a high molecular weight polymer of (KOH mg / g-resin) is particularly preferred.
  • These binder resins can be contained in an arbitrary amount in the photosensitive layer. However, when the amount exceeds 90% by mass, a preferable result is not obtained in terms of image strength formed using the layer. Therefore, it is preferably 10 to 90% by mass, more preferably 30 to 80% by mass. Further, the use ratio of the photopolymerizable compound and the binder resin is preferably in the range of 19 to 9/1 by weight, more preferably 2/8 to 82, and most preferably 3 / 7 ⁇ 7 3.
  • On-machine development type that removes the non-image area of the printing original plate by supplying dampening water and ink while rotating the cylinder without being developed after image formation.
  • a graph having an alkylene oxide chain on the side chain and an alkylene oxide chain on the main chain.
  • the block copolymer having is preferably used.
  • the alkylene oxide chain polyoxyethylene units and polyoxyethylene / polyoxypropylene units are preferable. Examples thereof include copolymers of polyethylene glycol monomethacrylate and other unsaturated group-containing compounds.
  • the binder resin used is a high molecular weight polymer having a weight average molecular weight of 5,000 to 300,000 and an alkylene oxide unit number average molecular weight of 500 to 10,000. Coalescence is particularly preferred.
  • These binder resins can be contained in an arbitrary amount in the photosensitive layer. However, when the amount exceeds 90% by mass, there are cases in which a favorable result is not obtained in terms of image strength formed using the layer. Therefore, it is preferably 10 to 90% by mass, more preferably 30 to 80% by mass.
  • the ratio of the photopolymerizable compound and binder resin used is 1 by weight.
  • the photosensitive layer of the present invention in order to prevent unnecessary ⁇ of the photopolymerizable compound during formation or storage of the photosensitive layer.
  • thermal polymerization inhibitor It is desirable to add a small amount of thermal polymerization inhibitor. Preferred thermal polymerization
  • ⁇ , Inhibitors include hydroquinone,. ⁇ -methoxyphenol, 1 t butyl 1 p-cresol, pyroga diol, 1 ptylcatel, benzoquinone, 4, 4 '-thiobis (3Methyl-6-t-bu Thiophenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosulphylhydroxylamine primary cerium salt, N-nitrosulphylhydroxylamine aluminum dium salt, etc. .
  • the amount of this type of thermal polymerization inhibitor added is preferably from about 0.01 to about 5% by weight based on the total components of the photosensitive layer.
  • higher fatty acid derivatives such as behenic acid and behenic acid amide are added, and the photopolymerizable photosensitive layer is subjected to a drying process after coating.
  • the surface may be unevenly distributed.
  • the addition amount of the higher fatty acid derivative is preferably 0.5 to 10% by mass of the total components of the photosensitive layer.
  • a colorant may be added for the purpose of coloring the photosensitive layer.
  • the colorant include phthalocyanine pigments (C. I. Pigmen t B l ue
  • pigments such as azo pigments, carbon black, titanium oxide, ethyl violet, crystal violet, azo dyes, anthraquinone dyes, cyanine dyes is there.
  • the addition amount of the dye and the pigment is preferably about 0.5% by mass to about 5% by mass of the total components of the photosensitive layer.
  • additives such as plasticizers such as inorganic filler, dioctyl phthalate, dimethyl phthalate, and glyceryl phosphate may be added.
  • plasticizers such as inorganic filler, dioctyl phthalate, dimethyl phthalate, and glyceryl phosphate
  • a known surfactant may be added for the purpose of improving the coating property of the coated surface.
  • surfactants include fluorine-based surfactants, polyoxyalkylene-based nonionic surfactants, silicon-based surfactants such as dialkylsiloxanes, and the like.
  • silica particles are preferable, and modified silica particles with improved surface characteristics are particularly preferable.
  • Silica particles are commonly used in the technical field and contain silicon dioxide (S i 0 2 ) as a main component.
  • the particle size of silica particles is usually 1 ⁇ ! ⁇ L OO Onm, preferably 1 ⁇ ! ⁇ 500 nm, more preferably in the range of 1 nm to 100 nm.
  • Silica particles are commercially available. For example, Snowtex 0L (particle size 45 ⁇ silica 20% colloid aqueous solution) and ST-ST (particle size 10-20nm silica 30% colloid Tyrethyl ketone solution) Nippon Aerosil Co., Ltd. AER0S IL 130 (particle size 16 nm silica), Mizusawa Chemical Co., Ltd. Mizukacil P-527U (particle size 60 nm silica) and the like.
  • Silica particles include forms such as fumed silica, precipitated silica, and colloidal silica. Among these, the use of colloidal silica is preferable.
  • the silica particles are used as modified silica particles by modifying the surface with an organic compound having at least one ethylenically unsaturated group, at least one hydrophilic site and at least one silyloxy group. It is preferable.
  • the ethylenically unsaturated group and the reactivity with the photopolymerizable compound are imparted, and the silyloxy group imparts the binding property to the silica particles.
  • the ethylenically unsaturated group and the silyloxy group are preferably located at both ends of the molecular chain of the organic compound. In this case, the hydrophilic portion exists between the ethylenically unsaturated group and the silyloxy group.
  • the hydrophilic site is not particularly limited, but is preferably a polyoxyalkylene chain, and may be any one of a polyethylene chain, a polypropylene chain, or a polyethylene-polyoxypropylene chain. Is preferred.
  • CH 2 CH-C00- (CH 2 CH 2 0) a- (CH 2 CH (CH 3 ) 0) strange— CO- X- (CH 2 ) .- (CHY) p- (CH 2 ) q -S i (OR) 3
  • R is an alkyl group of CiCe, preferably a methyl group or an ethyl group
  • X is a divalent organic group selected from —CH 2 —, 1 O—, 1 S—, and 1 NZ— (Z is H or ( ⁇ represents an alkyl group of ⁇ ), preferably Preferably H, ⁇
  • Y is an alkyl group of C j Ce or a halogen atom, preferably a methyl group or a fluorine atom,
  • n is an integer from 0 to 100, preferably an integer from 1 to 50
  • n is an integer from 0 to 100, preferably an integer from 0 to 20, provided that m + n is 1 or more
  • o is an integer of 0-10, preferably an integer of 1-10, p is an integer of 0-5, preferably an integer of 0-2,
  • Q is an integer from 0 to 10, preferably an integer from 1 to 10.
  • o + q is 1 or more, preferably 2 or more
  • the silyloxy group (_Si (0R) 3 ) reacts with the hydroxyl group on the silica surface and covalently bonds, so that the surface of the silica particle is modified.
  • Ethylene unsaturated groups bonded to the silica surface serve as reaction sites with the photopolymerizable compound.
  • the organic compound can be obtained, for example, by a reaction between polyethylene glycolate and 3-isocyanate propyltriethoxysilane.
  • the organic compound obtained by the reaction has the following structure.
  • the surface modification of the silica particles with the organic compound can be performed by a method commonly used in the technical field such as bringing both into contact with each other for a predetermined time.
  • the modification rate of the surface of the silica particles is usually in the range of 50 to 99%, preferably 80 to 99%.
  • the modification rate of the surface of the silica particles can be controlled by adjusting the weight ratio between the silica particles and the organic compound.
  • the photosensitive layer containing silica particles modified with the organic compound and the photopolymerizable compound is further improved in adhesion to the underlayer. Therefore, a photosensitive lithographic printing plate provided with the photosensitive layer on a support via a base layer has a support and a photosensitive layer even if the photopolymerizable compound in the photosensitive layer is crosslinked by exposure and the photosensitive layer contracts. And good integrity can be maintained.
  • the photosensitive layer in the photosensitive lithographic printing plate of the present invention can be obtained by dissolving the photosensitive composition containing the above-mentioned photopolymerizable compound in various organic solvents and coating it on the underlayer.
  • Solvents that can be used here include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, dimethyl ether, jetyl ether, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl.
  • Tyl ether Ethylene glycol dimethyl ether, Propylene glycol monomethyl ether, Propylene glycol monoethyl ether, Acetyl acetone, Cyclohexanone, Diacetone alcohol, Ethylene glycol monomethyl ether acetate, Ethylene glycol ether ether acetate, Ethylene glycol monoisopropyl Ether, Ethylene glycol monobutyl ether acetate, 3-Methoxypropanol, Methoxymethoxyethanol, Diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, Diethylene glycol dimethyl ether, Diethylene glycol dimethyl ether, Propylene glycol Monomethyl ether acetate, propylene glycol Allyl ether ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, ⁇ -leptylactolone, methyl lactate, ethyl lactate
  • the coating amount of the photosensitive layer in the photosensitive lithographic printing plate of the present invention is suitably in the range of 0.1 to 10 g / m 2 by weight after coating and drying, more preferably 0.3 to 5 g / m 2. And more preferably 0.5 to 3 g / m 2 .
  • the photosensitive lithographic printing plate of the present invention is usually exposed in the air, it is preferable to further provide a protective layer on the photosensitive layer.
  • the protective layer prevents the entry of low-molecular compounds such as oxygen and basic substances present in the atmosphere that inhibit the polymerization reaction in the photosensitive layer into the photosensitive layer, and facilitates exposure conditions in the atmosphere.
  • the desired properties of such a protective layer are low permeability of low-molecular compounds such as oxygen, and furthermore, good transparency of the irradiation light used for exposure and excellent adhesion to the photosensitive layer. And during development It can be easily removed.
  • the material for the protective layer examples include water-soluble high molecular compounds having relatively excellent crystallinity. Specifically, polyvinyl alcohol, polyvinyl pyrrolidone, acidic celluloses, gelatin, gum arabic, and polyacrylic acid. Etc. Of these, the use of polypinyl alcohol as the main component gives the best results for basic properties such as oxygen barrier properties and development removability.
  • the polyvinyl alcohol used for the protective layer may be partially substituted with an ester, an ether and an acetal as long as it contains an unsubstituted vinyl alcohol unit for having the necessary oxygen barrier properties and water solubility. Similarly, some of them may have other copolymer components.
  • polyvinyl alcohol examples include those that are 71-100% hydrolyzed and have a molecular weight in the range of 300-2400.
  • Kuraray Co., Ltd. PVA-105, PVA-1 10, PVA-1 17, PVA-1 17H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PV A-HC, PVA-203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-217E, PYA-220E, PVA-224E, PVA- 405, PVA-420, PVA-613, PVA-L8, etc.
  • Components of the protective layer selection of PVA type, use of additives, etc.), coating amount, etc. are selected considering oxygen barrier properties, development removability, capriability, adhesion, and scratch resistance. In general, the higher the hydrolysis rate of the PVA used,
  • a hydrophilic polymer made of polyvinyl alcohol is mixed with 20 to 60% by mass of an acrylic emulsion or a water-insoluble vinylpyrrolidone / vinyl acetate copolymer. The method of doing is mentioned.
  • the support for the photosensitive lithographic printing plate of the present invention may be any substrate as long as the surface is hydrophilic, but is preferably a dimensionally stable plate-like material such as paper, plastic (for example, polyethylene Paper laminated with polypropylene, polystyrene, etc., and also metals such as aluminum (including aluminum alloys), zinc, copper, etc.
  • plastic for example, polyethylene Paper laminated with polypropylene, polystyrene, etc., and also metals such as aluminum (including aluminum alloys), zinc, copper, etc.
  • an aluminum plate is particularly preferred because it is dimensionally significantly stable and inexpensive.
  • a composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in JP-B-48-18327 is also preferable. Usually the thickness is 0. 05 ⁇ ! About 1 mm.
  • It also has a surface of metal, especially aluminum; in the case of a support, graining treatment described later, sodium silicate, potassium fluoride zirconate It is preferable that a surface treatment such as an immersion treatment in an aqueous solution of phosphate or the like, or an anodizing treatment is performed.
  • Examples of the graining method include mechanical graining, chemical etching, and electrolytic grain as disclosed in JP-A-56-28893.
  • electrochemical graining method that electrochemically grains in hydrochloric acid or nitric acid electrolyte solution, and scratches aluminum surface with metal wire.
  • Wire-brush grain method pole grain that grinds aluminum surface with polishing ball and abrasive.
  • a mechanical graining method such as a brush grain method in which the surface is grained with a nylon brush and an abrasive can be used, and the above graining methods can be used alone or in combination.
  • the method of making the surface roughness usefully used in the present invention is an electrochemical method of graining chemically in hydrochloric acid or nitric acid electrolyte, and a suitable current density is 100 to 400 CZ dm 2 . It is a range. More specifically, electrolysis is performed in an electrolyte containing 0.1 to 50% hydrochloric acid or nitric acid under conditions of a temperature of 20 to 100 ° C, a time of 1 second to 30 minutes, and a current density of 100 to 400 C / dm 2. It is preferable to do so.
  • the grained aluminum support is chemically etched with acid or alkali.
  • acid When an acid is used as an etching agent, it takes time to destroy the fine structure, which is disadvantageous when the present invention is applied industrially, but it can be improved by using an alkali as the etching agent.
  • alkali agents examples include caustic soda, sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, potassium hydroxide, lithium hydroxide and the like.
  • concentration and temperature are 1 to The conditions are 50%, 20 to 100 ° C., and a condition that the dissolution flaw of aluminum is 5 to 20 g Z m 3 . After the etching, pickling is performed to remove the smudge remaining on the surface.
  • the acid used include nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, and borohydrofluoric acid.
  • the method for removing the smut after the electrochemical surface roughening treatment it is preferably 15 to 65 mass% at a temperature of 50 to 90 ° C. as described in JP-A-53-12739. Examples thereof include a method of contacting with sulfuric acid, and a method of re-etching by force described in Japanese Patent Publication No. 48-28123.
  • the surface roughness (Ra) of the aluminum support preferable in the present invention is' 0.3 to 0.7 m.
  • the aluminum support treated as described above is preferably further anodized.
  • the anodizing treatment can be performed by a method conventionally used in the technical field. Specifically, sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzene sulfonic acid, etc., or a combination of two or more of these, when direct current or alternating current is applied to aluminum in an aqueous solution or non-aqueous solution, An anodized film can be formed on the surface of the aluminum support.
  • the conditions of the anodizing treatment vary depending on the electrolyte used and cannot be determined in general.
  • the electrolyte concentration is 1 to 80%, and the solution temperature is 5 to 70 ° (: A current density of 0.5 to 60 amps Zdm 2 , a voltage of 1 to 100 V, and an electrolysis time of 10 to 100 seconds are suitable.
  • the anodic oxide film is preferably 1 to 10 g.Zm 2 , and if it is less than 1 g / m 2 , the plate is easily damaged, and 10 g / m 2 Exceeding this requires a lot of power for manufacturing, which is economically disadvantageous.
  • it is 1.5-7 g / m 2 , more preferably 2-5 g Z m 2 .
  • the support may be subjected to sealing treatment after graining treatment and anodizing.
  • sealing treatment is performed by immersing the substrate in a hot aqueous solution containing hot water and an inorganic salt or an organic salt, and a steam bath.
  • the support is preferably subjected to a treatment with an alkali metal silicate after the graining treatment and the anodization.
  • a treatment with an alkali metal silicate metal salt here means that the support is immersed in the alkaline silicate metal aqueous solution for a predetermined time.
  • the preferable treatment time is 1 second to 2 minutes
  • the preferred alkali metal silicate aqueous solution temperature is 40 to 90 ° C.
  • the concentration of the aqueous solution is 1 g / 1 to 50 g Zl.
  • the alkali metal silicate include sodium silicate, potassium silicate, and lithium silicate.
  • a base layer is formed on a support (in the case of aluminum, aluminum that has been appropriately surface-treated as described above), and then a photosensitive layer comprising the above-described components is applied,
  • a photosensitive lithographic printing plate can be formed by applying a protective layer if necessary.
  • the photosensitive lithographic printing plates obtained in this way are Ar lasers, second harmonics of semiconductor lasers (SHG-LD, 350-600 nm), YAG-SHG lasers, InGaN-based short-wave semiconductor lasers, etc.
  • High-power lasers with maximum intensity in the near-infrared to infrared region are preferably used so that they can be developed after being directly exposed to light, but can be handled in a bright room.
  • the As such a laser having the maximum intensity from the near infrared to the infrared region various lasers having the maximum intensity in the wavelength region of 760 to 1,200 nm are used.
  • a heating process for 1 second to 5 minutes at a temperature of 50 ° C to 150 ° C is provided for the purpose of increasing the curing rate of the photopolymerizable photosensitive layer after image exposure and development. Also good.
  • alkaline aqueous solution As the developer used for such development processing, a conventionally known alkaline aqueous solution can be used.
  • Inorganic alkaline agents such as potassium, the same ammonium, sodium borate, the same potassium, the same ammonium, the sodium hydroxide, the same ammonium, the same potassium, and the same lithium.
  • Organic alkali agents such as diisopropanolamine, ethylenimine, ethylenediamine and pyridine may be used in combination. These alkaline agents are used alone or in combination of two or more.
  • surfactants described below may be added to the developer.
  • Other surfactants include, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl.
  • Polyoxyethylene alkyl such as phenyl ether Polyarylethylenes, polyoxyethylene alkyl esters such as polyoxyethylene stearate, sorbitan monolaurate, sorbitan monostearate, sorbitan distearate, sorbitan monostearate, sorbitan sesquioleate, sorbitan tri
  • Nonionic surfactants such as sorbate alkyl esters such as oleate, monodarlysyl alkyl esters such as glycerol monostearate and glycerol monooleate; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, butylnaphthalene Alkylnaphthalenes such as sodium sulfonate, sodium pentylnaphthalenesulfonate, sodium hexylnaphthalenesulfonate, sodium octanenaphthalenesulfonate An
  • R 1 is an optionally substituted alkyl group having 3 to 15 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 15 carbon atoms, or A C4-C15 heteroaromatic cyclic group which may have a substituent (as the substituent, an alkyl group having 1 to 20 carbon atoms, a halogen atom such as Br, Cl, or I, a carbon number of 6 to Examples include 15 aromatic hydrocarbon groups, aralkyl groups having 7 to 17 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, alkoxy monocarbonyl groups having 2 to 20 carbon atoms, and acyl groups having 2 to 15 carbon atoms.
  • R 2 Is an alkylene group having 1 to 10 carbon atoms which may have a substituent (the substituent includes an alkyl group having 1 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 15 carbon atoms).
  • n represents an integer from 1 to 100 ⁇ .
  • the agents can be used alone or in combination. Further, the content of these surfactants in the developer is preferably 0.1 to 20% by mass in terms of active ingredients.
  • benzoic acid phthalic acid, P—ethyl benzoic acid, p— n —propyl benzoic acid, p —isopropyl benzoic acid, p — n —butyl benzoic acid, p—t—butyl benzoic acid, p — 2— Hydroxychetyl benzoic acid, decanoic acid, salicylic acid, 3-hydroxy-2-carboxylic acid such as naphthoic acid; isopropyl alcohol, benzyl alcohol, ethyl acetate sorb, butyl cellosolve, phenolic solvate, propylene glycol, diacetone Organic solvents such as alcohol; in addition, chelating agents, reducing agents, dyes, pigments, water softeners, preservatives, antifoaming agents, etc.
  • the development of the photosensitive lithographic printing plate of the present invention with the developer is performed at a temperature of O to 60 ° C., preferably about 15 to 40 ° C., for example, by exposure. Dip in a developer and rub with a brush. Furthermore, development processing may be performed using an automatic developing machine, in which case the developer will become fatigued depending on the amount of processing. The processing capability may be restored using a developer.
  • a protective layer is provided on the photosensitive layer, the protective layer may be removed and the unexposed portion of the photosensitive layer may be removed at the same time using the developer, or water, The protective layer may be removed first with warm water, and then the unexposed photosensitive layer may be removed with a developer.
  • These water or warm water can contain, for example, a preservative described in JP-A-10-10754, an organic solvent described in JP-A-8-278636, and the like.
  • the photosensitive lithographic printing plate thus developed is preferably described in JP-A Nos. 54-8002, 55-115045, 59-58431, etc. It is post-treated with a desensitizing solution containing rinse water, a rinsing solution containing a surfactant and the like, arabia gum, starch derivatives and the like. In the post-treatment of the photosensitive lithographic printing plate of the present invention, these treatments can be used in various combinations.
  • the printing plate obtained by the above treatment can be improved in printing durability by a known post-exposure treatment or heat treatment such as burning.
  • the lithographic printing plate obtained by the above processing is loaded on an offset printing press and used for printing a large number of sheets.
  • the obtained photosensitive lithographic printing plate is also called “on-press development type”.
  • the obtained photosensitive lithographic printing plate is used for a plate that can be attached to the printing press plate cylinder and started printing after imagewise exposure. I can do it.
  • HEMA hydroxychetyl methacrylate
  • r VTMSj vinyltrimethyoxysilane
  • the aluminum substrate subjected to brush roughening and sulfuric acid anodization was previously treated with an aqueous sodium silicate solution, and then treated with an aqueous solution (2 gZl) of vinyl silane polymer 14 heated to 60 ° C. Specifically, the above substrate was immersed in the above aqueous solution for 20 seconds, and then the substrate was washed with deionized water and then dried at 100 ° C. for 90 seconds.
  • the aluminum substrate subjected to brush roughening and sulfuric acid anodization was previously treated with an aqueous solution of sodium silicate, and then treated with an aqueous solution of polymer 5-7 heated to 60C (2 g / 1). Specifically, the above substrate was immersed in the above aqueous solution for 20 seconds, and then the substrate was washed with deionized water and then dried at 100 ° C. for 90 seconds.
  • the above solution was applied using a wire winding No. 26 rod and dried for about 90 seconds in a conveyor open set to 100 ° C.
  • DESMODUR N 3200 aliphatic polyisocyanate resin based on hexamethylene diisocyanate, manufactured by Bayer
  • 2-amino-4-hydroxy-6-methylpyrimidine 2-amino-4-hydroxy-6-methylpyrimidine
  • the photosensitive lithographic printing plate produced in “Manufacture of photosensitive lithographic printing plate 1” was evaluated for the adhesion of the photosensitive layer to the substrate, ink smear resistance during printing, and developability. The results are shown in Table 3. Image formation was carried out using a Creo Trend Setting 1244, a drum speed of 90 rpm, and a setting power of 10 W (225 mJ / cn 2 ). Each of the above characteristics was performed by manually linking in the laboratory. In other words, the imaged lithographic printing plate was washed with 1% IPA and 1% NA-10 8W (a fountain solution made by Dainippon Ink & Chemicals, Inc.), a part of which was a cloth containing ink.
  • 1% IPA and 1% NA-10 8W a fountain solution made by Dainippon Ink & Chemicals, Inc.
  • Komori S-26 Komo ri S-26
  • Roland R-200 as printing machines
  • DIC GEOS-G N grade as ink Oji Paper Co., Ltd. Royal Coat 44.5 kgZ A
  • dampening water As a blanket, DIC K-705 1% + IPA 10% aqueous solution and DIC NA-108W 1% + IPA 1% were used in the printing test.
  • DIC K-705 1% + IPA 10% aqueous solution DIC NA-108W 1% + IPA 1%
  • the non-image area of the plate should be finished after 10 rotations of the dampening roll, and the image area should be fully inked after 30 sheet printings. Should be accepted. If these characteristics are not impaired by the printing test, printability is acceptable.
  • the drum speed was set to 150 rpm and the setting power was set to 10 W (120 mJ / cm 2 ) Set to Then, image formation was performed.
  • Each imaged lithographic printing plate was developed by KPG plate opener PK-910 using a developer containing 14 parts PD-1 + 140 parts water + 40 parts NBL.
  • the photosensitive lithographic printing plate of the present invention Since the photosensitive lithographic printing plate of the present invention has good adhesion between the photosensitive layer and the support, it has excellent printing durability and can improve the printing life of the lithographic printing plate. In addition, the photosensitive lithographic printing plate of the present invention also has good ink stain resistance.

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Abstract

L’invention concerne une plaque d’impression lithographique photosensible comprenant un corps de soutien et une couche photosensible contenant un composé photopolymérisable. Cette plaque d’impression lithographique polymérisable est caractérisée en ce qu’elle possède une couche de base disposée entre la couche photosensible et le corps de support et qu’elle contient un (co)polymère ayant une unité constitutionnelle incluant un groupe non saturé sur le plan éthylénique lié à un atome de silicium et à un groupe d’acide phosphonique.
PCT/JP2006/305619 2005-03-30 2006-03-15 Plaque d’impression lithographique photosensible WO2006109454A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP06729586A EP1865378A4 (fr) 2005-03-30 2006-03-15 Plaque d impression lithographique photosensible
US11/817,876 US7883830B2 (en) 2005-03-30 2006-03-15 Photosensitive planographic printing plate
CN2006800096652A CN101167017B (zh) 2005-03-30 2006-03-15 感光性平版印刷版

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JP4690090B2 (ja) 2011-06-01
CN101167017B (zh) 2011-04-13
US20080280228A1 (en) 2008-11-13
EP1865378A4 (fr) 2009-07-15
EP1865378A1 (fr) 2007-12-12
JP2006276768A (ja) 2006-10-12
CN101167017A (zh) 2008-04-23
US7883830B2 (en) 2011-02-08

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